Process for graft polymerization on polymer surfaces using organo-borane-amine complexes as radical initiators

Abstract

The present invention relates to a process for the modification of a polymer surface. The polymer surface is treated with (i) an organoborane-amine complex and subsequently with (ii) a radically polymerizable monomer compound and optionally a deblocking agent.

1 - 13 . (canceled) 
     
     
         14 . A process for the modification of a polymer surface comprising treating a polymer surface with
 (i) an organoborane-amine complex and subsequently with   (ii) a radically polymerizable monomer compound and optionally a deblocking agent.   
     
     
         15 . The process according to  claim 14 , wherein any excess polymerized material that is not grafted onto the surface is removed. 
     
     
         16 . The process according to  claim 14 , wherein the polymer has a low surface energy. 
     
     
         17 . The process according to  claim 14 , wherein the organoborane-amine complex has a structure of formula (1)
   R 1 R 2 R 3 B—NR 4 R 5 R 6    (1),
   wherein R 1 , R 2  and R 3  are independently alkyl, aryl, alkoxy or aryloxy groups, with the proviso that at least one of R 1 , R 2  and R 3  is an alkyl or aryl group, and   R 4 , R 5  and R 6  are independently hydrogen, alkyl, cycloalkyl, substituted alkyl, alkoxy, alkylamino, aryl or heteroaryl groups, with the proviso that not more than two of R 4 , R 5  and R 6  are simultaneously hydrogen, or   NR 4 R 5 R 6  is a heterocyclic aliphatic or aromatic amine, optionally comprising further heteroatoms selected from the group, consisting of N, O, S and P.   
     
     
         18 . The process according to  claim 17 , wherein the organoborane-amine complex is a trialkylborane-amine complex. 
     
     
         19 . The process according to  claim 14 , wherein the radically polymerizable monomer compound has a structure of formula (2) comprising an olefinic double bond
   R 7 R 8 C═CR 9 R 10    (2),
   or with a structure of formula (3) comprising an acetylenic triple bond
   R 7 C≡CR 8    (3),
 
   or with a structure of formula (4) comprising a carbonyl group 
   R 7 R 8 C═O   (4),
 
   or with a structure of formula (5) comprising a carbon nitrogen double bond
   R 7 R 8 C═NR 9    (5),
 
   wherein R 7 , R 8 , R 9  and R 10  are independently for example hydrogen, alkyl, cycloalkyl, substituted alkyl, aralkyl, alkaryl, alkoxy, alkylamino, aryl or heteroaryl, carbonyl, carboxyl, amide, ester or nitrile groups.   
     
     
         20 . The process according to  claim 14 , wherein the radically polymerizable monomer compound is ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, styrene, acrylic acid, methacrylic acid, an acrylic or methacrylic acid ester, acrylonitrile, vinyl acetate, 2-hydroxyethylmethacrylate (HEMA), [2-(methacryloyloxy)ethyl]trimethylammonium chloride (QAEMA), glycidyl methacrylate (GMA), diallyldimethylammonium chloride (DADMA), 1-vinyl-2-pyrrolidinone (NVP) or N-dodecyl(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium bromide (QAEMA-C12) or mixtures thereof. 
     
     
         21 . The process according to  claim 14 , wherein the deblocking agent is a mineral or an organic acid. 
     
     
         22 . The process according to  claim 16 , wherein the low surface energy polymer has a contact angle or from 90° to 180°. 
     
     
         23 . The process according to  claim 16 , wherein the low surface energy polymer is polydimethylsiloxane (PDMS), polyethylene (PE), polypropylene (PP), polytetrafluorethylene (PTFE) or polystyrene (PS). 
     
     
         24 . The process according to  claim 14 , wherein the organoborane-amine complex is applied in solution at a concentration in the range of from 0.5 to 60% (v/v). 
     
     
         25 . The process according to  claim 14 , wherein the radically polymerizable monomer compound is applied in solution at a concentration in the range of from 1 to 75% (v/v). 
     
     
         26 . The process according to  claim 25 , wherein the solution comprises water.